CN104231432A - Method for preparing high-melt-flow-rate polypropylene by virtue of polypropylene T30s aggregate modification - Google Patents

Method for preparing high-melt-flow-rate polypropylene by virtue of polypropylene T30s aggregate modification Download PDF

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Publication number
CN104231432A
CN104231432A CN201410467374.4A CN201410467374A CN104231432A CN 104231432 A CN104231432 A CN 104231432A CN 201410467374 A CN201410467374 A CN 201410467374A CN 104231432 A CN104231432 A CN 104231432A
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polypropylene
modification
pellet
flow rate
melt flow
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CN104231432B (en
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杨金明
王波
田小艳
任蕊
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Shaanxi Yanchang Petroleum Group Co Ltd
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Shaanxi Yanchang Petroleum Group Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00Processes of treating or compounding macromolecular substances
    • C08J3/20Compounding polymers with additives, e.g. colouring
    • C08J3/22Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0033Additives activating the degradation of the macromolecular compound
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/09Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098Metal salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/13Phenols; Phenolates
    • C08K5/134Phenols containing ester groups
    • C08K5/1345Carboxylic esters of phenolcarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/14Peroxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/524Esters of phosphorous acids, e.g. of H3PO3
    • C08K5/526Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10Homopolymers or copolymers of propene
    • C08J2323/12Polypropene

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

The invention discloses a method for preparing high-melt-flow-rate polypropylene by virtue of polypropylene T30s aggregate modification, belongs to the technical field of production of special materials for polypropylene modification, and in particular relates to a method for obtaining a polypropylene coating material compound by modifying the polypropylene T30s aggregate. An isoparaffin solution of 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-trinonane peroxide serves as a degradation agent. Because the method is initiated by adopting the isoparaffin solution of 3,6,9-triethyl-3,6,9-trimethyl-1,4,7-trinonane peroxide, toxic or odorous harmful substances are not generated after decomposition, so that the reaction is uniform and stable, and the product is extremely high in quality and high in stability. The product has the characteristics of molecular weight distribution of less than 3, small coating shrinkage, high yield and odorlessness.

Description

The method of high melt flow rate polypropylene is prepared in the modification of a kind of polypropylene T30s pellet
Technical field
The invention belongs to polypropylene modification PP Pipe Compound production technical field, be specifically related to a kind of method of polypropylene T30s pellet being carried out to modification acquisition polypropylene coating material composition.
Background technology
The melt flow rate (MFR) of polypropylene own is not high, and relative molecular mass is higher, relative molecular mass distribution is wider, poor processability.But polypropylene is through modified, melt flow rate (MFR) and surface-coated performance are improved all significantly, therefore can be widely used in the coating of the wrapping material such as woven bag, two-way holder stretched polypropylene overlay film, medicine, there is the advantages such as stripping strength is good, heat sealability is good, good flowing properties.
Directly be coated on woven bag by polypropylene salivation film, add intensity and the overall performance of woven bag, manufacturing cost also declines to some extent.And there is the features such as intensity is high, bonding force strong, good fluidity, film forming are even, waterproof, protection against the tide, along with the development of domestic packaging industry, high melt flow rate polypropylene use range and usage quantity progressively expand, and market demand increases day by day.
But the at present conventional simple peroxide agent initiator system containing phenyl ring, can produce in production process and product that peculiar smell is excessively difficult to remove, problem that product contains poisonous residual, molecular weight distribution index higher (being greater than 3).
Summary of the invention
The object of the invention is to propose a kind of 3,6,9-triethyl-3,6,9-trimethylammonium-Isosorbide-5-Nitrae, the iso-alkane solution of 7-tri-peroxide nonane causes, to the modification of polypropylene T30s pellet degradation, obtain melt flow rate (MFR) and reach the method for the high melt flow rate polypropylene of 15-40 g/10min, have that molecular weight distribution is little, film shrink little, productive rate is high, the feature of free from extraneous odour.
To achieve these goals, the technical solution used in the present invention is as follows:
A method for high melt flow rate polypropylene is prepared in the modification of polypropylene T30s pellet, and use 3,6,9-triethyl-3,6,9-trimethylammoniums-Isosorbide-5-Nitrae, the iso-alkane solution of 7-tri-peroxide nonane is as degradation agents.
Preferably, described isoparaffin is C12-20 isoparaffin.
More preferably, 3,6,9-triethyl-3,6,9-trimethylammonium-Isosorbide-5-Nitrae, isoparaffin (C12-20) solution of 7-tri-peroxide nonane is by 0.05-0.2 mass parts 3,6,9-triethyl-3,6,9-trimethylammonium-Isosorbide-5-Nitrae, 7-tri-peroxide nonane to be dissolved in 1-2 mass parts isoparaffin and to mix acquisition.
Further preferably, the method for high melt flow rate polypropylene is prepared in the modification of a kind of polypropylene T30s pellet, comprising:
The first step, mixes polypropylene T30s pellet, antioxidant and calcium stearate, obtains masterbatch;
Second step, mixes polypropylene T30s pellet with masterbatch, obtains compound;
3rd step, by 3,6,9-triethyl-3,6,9-trimethylammoniums-Isosorbide-5-Nitrae, the isoparaffin of 7-tri-peroxide nonane is pumped in forcing machine second heating module, is joined in forcing machine by compound and extrudes blank.
Wherein preferably, polypropylene T30s pellet in the first step, the mass ratio of antioxidant and calcium stearate is 88 ~ 97:1 ~ 5:1 ~ 5.
In second step, the mass ratio of polypropylene T30s pellet and masterbatch is 50:1-3.
3,6,9-triethyl-3,6,9-trimethylammoniums-Isosorbide-5-Nitraes in 3rd step, the iso-alkane solution of 7-tri-peroxide nonane and the mass ratio of compound are 95-98:1.05-2.2.
Described antioxidant is mixed by antioxidant 1010 and irgasfos 168.Especially preferred is that the antioxidant 1010 of 1:1 and irgasfos 168 mix by mass ratio.
Or be preferably, compound is fed in raw material by twin screw extruder first paragraph cylindrical shell spout, from the 3rd section of cylindrical shell in the 3rd step, temperature setting 200-260 DEG C, material residence time 15-30 second in forcing machine, screw speed 200-600rpm, extrudes pelletizing.
Because the present invention adopts 3,6,9-triethyl-3,6,9-trimethylammoniums-Isosorbide-5-Nitrae, the iso-alkane solution of 7-tri-peroxide nonane causes, and do not produce the poisonous objectionable impurities having peculiar smell after decomposition, reaction can be made uniform and stable, and quality product is very high, and product stability is good.Have that molecular weight distribution is less than 3, film shrink little, productive rate is high, the feature of free from extraneous odour.
Embodiment
Below in conjunction with embodiment, production method of the present invention is described in further detail.
Embodiment one
The first step, mixes 92g polypropylene T30s pellet with 1g composite antioxidant (1010+168) (mass ratio 1:1), 1g calcium stearate, stirring at low speed 5-15min, obtains masterbatch;
Second step, drops in high-speed mixer by 100g polypropylene T30s pellet and 2g masterbatch, high-speed mixing 5-20min, obtains compound;
3rd step, unlatching twin screw extruder, get dried 98g compound and evenly fed by hopper, from the 3rd section of cylindrical shell, temperature sets 260 DEG C, and material is 30 seconds residence time in forcing machine, screw speed 200rpm;
4th step, by 0.05g3,6,9-triethyl-3,6,9-trimethylammonium-1,4,7-tri-peroxide nonane is dissolved in 1g C12-20 isoparaffin and mixes, and is pumped into from forcing machine second heating module by volume pump, superoxide is decomposed completely, adopt vacuum take-off in the last heating zone of die head, extrude pelletizing, namely obtain high melt flow rate polypropylene.
After testing, melt flow rate (MFR) reaches 17 g/10min, molecular weight distribution index is 2.5, productive rate for for 99.9%, free from extraneous odour.
 
Embodiment two
The first step, mixes 88g polypropylene T30s pellet with 3g composite antioxidant (1010+168) (mass ratio 1:1), 3g calcium stearate, stirring at low speed 10min, obtains masterbatch;
Second step, by 100 gpolypropylene T30s pellet and 4g masterbatch drop in high-speed mixer, high-speed mixing 5-20min, obtain compound;
3rd step, unlatching twin screw extruder, get dried 97g compound and evenly fed by hopper, from the 3rd section of cylindrical shell, temperature sets 240 DEG C, and material is 20 seconds residence time in forcing machine, screw speed 400rpm;
4th step, by 0.01g 3,6,9-triethyl-3,6,9-trimethylammonium-1,4,7-tri-peroxide nonane is dissolved in 1.5g C12-20 isoparaffin and mixes, and is pumped into from forcing machine second heating module by volume pump, superoxide is decomposed completely, adopt vacuum take-off in the last heating zone of die head, extrude pelletizing, namely obtain high melt flow rate polypropylene.
Melt flow rate (MFR) reaches 30 g/10min, molecular weight distribution index is 2.2, productive rate for for 99.9%, free from extraneous odour.
 
Embodiment three
The first step, mixes 97g polypropylene T30s pellet with 5g composite antioxidant (1010+168) (mass ratio 1:1), 5g calcium stearate, stirring at low speed 5min, obtains masterbatch;
Second step, drops in high-speed mixer by 100g polypropylene T30s pellet and 6g masterbatch, high-speed mixing 5min, obtains compound;
3rd step, unlatching twin screw extruder, get dried 95g compound and evenly fed by hopper, from the 3rd section of cylindrical shell, temperature sets 200 DEG C, and material is 15 seconds residence time in forcing machine, screw speed 600rpm;
4th step, by 0.2g 3,6,9-triethyl-3,6,9-trimethylammonium-1,4,7-tri-peroxide nonane is dissolved in 2g C12-20 isoparaffin and mixes, and is pumped into from forcing machine second heating module by volume pump, superoxide is decomposed completely, adopt vacuum take-off in the last heating zone of die head, extrude pelletizing, namely obtain high melt flow rate polypropylene.
Melt flow rate (MFR) reaches 40 g/10min, molecular weight distribution index is 2.1, productive rate for for 99.9%, free from extraneous odour.

Claims (10)

1. a method for high melt flow rate polypropylene is prepared in the modification of polypropylene T30s pellet, it is characterized in that: use 3,6,9-triethyl-3,6,9-trimethylammoniums-Isosorbide-5-Nitrae, the iso-alkane solution of 7-tri-peroxide nonane is as degradation agents.
2. the method for high melt flow rate polypropylene is prepared in a kind of polypropylene T30s pellet according to claim 1 modification, it is characterized in that described isoparaffin is the isoparaffin of C12-20.
3. the method for high melt flow rate polypropylene is prepared in a kind of polypropylene T30s pellet according to claim 2 modification, it is characterized in that 3,6,9-triethyl-3,6,9-trimethylammonium-1,4, the iso-alkane solution of 7-tri-peroxide nonane is by 0.05-0.2 mass parts 3,6,9-triethyl-3,6,9-trimethylammonium-Isosorbide-5-Nitrae, 7-tri-peroxide nonane to be dissolved in 1-2 mass parts isoparaffin and to mix acquisition.
4. the method for high melt flow rate polypropylene is prepared in a kind of polypropylene T30s pellet modification according to claim 1 or 2 or 3, it is characterized in that comprising:
The first step, mixes polypropylene T30s pellet, antioxidant and calcium stearate, obtains masterbatch;
Second step, mixes polypropylene T30s pellet with masterbatch, obtains compound;
3rd step, by 3,6,9-triethyl-3,6,9-trimethylammoniums-Isosorbide-5-Nitrae, the isoparaffin of 7-tri-peroxide nonane is pumped in forcing machine second heating module, is joined in forcing machine by compound and extrudes blank.
5., as the method for high melt flow rate polypropylene is prepared in a kind of polypropylene T30s pellet according to claim 4 modification, it is characterized in that polypropylene T30s pellet in the first step, the mass ratio of antioxidant and calcium stearate is 88 ~ 97:1 ~ 5:1 ~ 5.
6., as the method for high melt flow rate polypropylene is prepared in a kind of polypropylene T30s pellet according to claim 4 modification, it is characterized in that the mass ratio of polypropylene T30s pellet and masterbatch in second step is 50:1-3.
7. as the method for high melt flow rate polypropylene is prepared in a kind of polypropylene T30s pellet according to claim 4 modification, to it is characterized in that in the 3rd step 3,6,9-triethyl-3,6,9-trimethylammonium-Isosorbide-5-Nitrae, the iso-alkane solution of 7-tri-peroxide nonane and the mass ratio of compound are 95-98:1.05-2.2.
8., as the method for high melt flow rate polypropylene is prepared in a kind of polypropylene T30s pellet according to claim 4 modification, it is characterized in that described antioxidant is mixed by antioxidant 1010 and irgasfos 168.
9., as the method for high melt flow rate polypropylene is prepared in a kind of polypropylene T30s pellet according to claim 4 modification, it is characterized in that the mass ratio of antioxidant 1010 and irgasfos 168 is 1:1.
10. as the method for high melt flow rate polypropylene is prepared in a kind of polypropylene T30s pellet according to claim 4 modification, it is characterized in that it being fed in raw material by twin screw extruder first paragraph cylindrical shell spout by compound in the 3rd step, from the 3rd section of cylindrical shell, temperature setting 200-260 DEG C, material residence time 15-30 second in forcing machine, screw speed 200-600rpm, extrudes pelletizing.
CN201410467374.4A 2014-09-15 2014-09-15 Method for preparing high-melt-flow-rate polypropylene by virtue of polypropylene T30s aggregate modification Active CN104231432B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104626510A (en) * 2015-01-16 2015-05-20 湖南盛锦新材料有限公司 Double-screw extruder suitable for melt-blown nonwoven cloth special material production
CN112574511A (en) * 2020-12-22 2021-03-30 陕西省石油化工研究设计院 Special material for centrifugally blowing polypropylene and preparation method thereof
CN112795097A (en) * 2021-01-05 2021-05-14 中广核俊尔(浙江)新材料有限公司 High-flexibility low-odor polypropylene material, preparation method thereof and application thereof in manufacturing melt-blown fabric
CN115947978A (en) * 2022-12-13 2023-04-11 江苏极易新材料有限公司 Compounding agent granulation method with melt finger control for polyolefin

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104626510A (en) * 2015-01-16 2015-05-20 湖南盛锦新材料有限公司 Double-screw extruder suitable for melt-blown nonwoven cloth special material production
CN104626510B (en) * 2015-01-16 2017-12-01 湖南盛锦新材料有限公司 Suitable for the double screw extruder of melt spraying non-woven fabrics PP Pipe Compound production
CN112574511A (en) * 2020-12-22 2021-03-30 陕西省石油化工研究设计院 Special material for centrifugally blowing polypropylene and preparation method thereof
CN112795097A (en) * 2021-01-05 2021-05-14 中广核俊尔(浙江)新材料有限公司 High-flexibility low-odor polypropylene material, preparation method thereof and application thereof in manufacturing melt-blown fabric
CN115947978A (en) * 2022-12-13 2023-04-11 江苏极易新材料有限公司 Compounding agent granulation method with melt finger control for polyolefin

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